Aryloxy-phthalocyanines of group iv metals

ABSTRACT

The present disclosure relates to a compound comprising an aryloxy-phthalocyanine compound of group IV metals, a method for preparing said compound and an article of manufacture made therefrom.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/197,903 filed Mar. 5, 2014, which claims the benefit of U.S.Provisional Application No. 61/776,220 filed Mar. 11, 2013. The contentsof the referenced application(s) are incorporated into the presentapplication by reference.

BACKGROUND OF THE INVENTION

A. Field of the Invention

The present disclosure relates to compositions comprising anaryloxy-phthalocyanine compound of a group IV metal, methods forpreparing said compositions, and articles of manufacture made therefrom.

B. Description of Related Art

Organic materials can be used, for example, as semiconductors inlow-cost photovoltaic cells. Organic materials can offer significantadvantages in terms of materials and manufacturing cost relative toexisting silicon technologies, and they do not typically suffer fromsupply demand pressures of the marketplace common to silicon. Currentstate of the art molecular based thin film devices can exhibitefficiencies similar to those of polymer based cells; however, organicthin film solar cells provide a significant advantage due to their easeof manufacture. Organic thin film solar cells do not necessarily utilizesolution-processing methods employed for polymer-based cells. Instead,they typically use vacuum deposition methods that can be scalable andrelatively cheap to implement. Such a device structure has the advantagethat formation of a nano-phase separated bulk heterojunction filmstructure is not required.

Currently available organic semiconductors prepared using conventionalmethods generally suffer from low charge carrier mobility or electricalconduction. Additionally, in the case of small molecules, batch to batchvariations are commonly observed in both film forming properties andelectrical performance. It is therefore desirable to obtain new organicsemiconducting materials having performance properties that can betuned, optimized or engineered through molecular variation. These needsand other needs are satisfied by the compositions and methods of thepresent disclosure.

SUMMARY OF THE INVENTION

This invention relates generally to aryloxy-phthalocyanine compounds,methods for preparing said compounds, and articles of manufacture madetherefrom. In one aspect, the aryloxy-phthalocyanine compound comprisesvarious aryloxy molecular fragments and group IV metals.

Described herein is a compound of a general molecular structure (I):

wherein M is one or more group IV metals and comprises silicon,germanium, tin, or a combination thereof wherein “n” is an integer equalto or greater than 0; wherein each R₁ independently comprises a straightchain alkyl group, a branched alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an alkoxy group, an aryloxy group,heterocyclic group, a monocyclic aromatic group, a polycyclic aromaticgroup, an aryl, an alkylaryl group, an arylalkyl group, an akylenegroup, a hydrogen, a halogen, or a combination thereof and wherein R₂comprises an aryl containing group comprising from greater than or equalto about 6 to about 22 carbon atoms, wherein the aryl containing groupcan optionally be substituted at any one or more positions by one ormore heteroatoms, wherein the heteroatom, if present, can comprise ahalogen, oxygen, sulfur, nitrogen, or a combination thereof.

In yet another aspect, described herein is a compound having the generalstructure (II):

wherein M is one or more group IV metals and comprises silicon,germanium, tin, or a combination thereof wherein “n” is an integer equalto or greater than 0; wherein each R₁ independently comprises a straightchain alkyl group, a branched alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an alkoxy group, an aryloxy group,heterocyclic group, a monocyclic aromatic group, a polycyclic aromaticgroup, an aryl group, an alkylaryl group, an arylalkyl group, an akylenegroup, a hydrogen, a halogen, or a combination thereof and wherein R₂and R₃ are the same or different and can independently comprise ahalogen, oxygen, sulfur, nitrogen, aryl or an aryloxy containing groupcomprising from greater than or equal to about 6 to about 22 carbonatoms, wherein the aryl containing group can optionally be substitutedat any one or more positions by one or more heteroatoms, wherein theheteroatom, if present, can comprise a halogen, oxygen, sulfur,nitrogen, or a combination thereof.

In yet another aspect, described herein is a method for preparing acompound having the general structure (I), the method comprising: (a)providing a compound comprising a halogen-metal bond containing R₁substituted phthalocyanine precursor, wherein the halogen compriseschloride, bromine, iodine, fluorine, or a combination thereof, andwherein each R₁ comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; (b) providing a reactant comprising optionallysubstituted aryl containing (—R₂) and/or optionally substitutedarylalcohol containing groups (OH—R₂), wherein R₂ comprises from greaterthan or equal to about 6 to about 22 carbon atoms, wherein the reactant,if substituted, can be substituted at one or more positions by one ormore heteroatoms comprising halogen, oxygen, sulfur, nitrogen, or acombination thereof; and (c) reacting the compound comprising ahalogen-metal bond containing phthalocyanine precursor and the reactantin the presence of an organic solvent under conditions effective to formthe compound of the general molecular structure (I), wherein thecompound of the general molecular structure (I) is non-soluble,negligibly soluble, partially soluble in an organic solvent, or at leastpartially soluble in an organic solvent.

In yet another aspect, described herein is a method for preparing acompound having the general structure (II), the method comprising: (a)providing a compound comprising a halogen-metal bond containing R₁substituted phthalocyanine precursor, wherein the halogen compriseschlorine, bromine, iodine, fluorine, or a combination thereof, andwherein each R₁ comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; (b) providing a reactant comprising R₂ and/or R₃moieties, wherein R₂ and R₃ are the same or different and canindependently comprise halogen, oxygen, sulfur, nitrogen, and/or anoptionally substituted aryloxy containing group comprising from greaterthan or equal to about 6 to about 22 carbon atoms, wherein the aryloxygroup, if substituted, can be substituted at one or more positions byone or more heteroatoms comprising a halogen, oxygen, sulfur, nitrogen,or a combination thereof; and (c) reacting the compound comprising ahalogen-metal bond containing phthalocyanine precursor and the reactantin the presence of an organic solvent under conditions effective to formthe compound of the general structure (II), wherein the compound of thegeneral structure (II) is non-soluble, negligibly soluble, partiallysoluble in an organic solvent, or at least partially soluble in anorganic solvent.

In a further aspect, a photovoltaic cell is disclosed, wherein aphotoactive region comprises a small molecule organic semiconductorcomprising an aryloxy-phtalocyanine of group IV metals comprising acompound of a general formula (I):

wherein M is one or more group IV metals and comprises silicon,germanium, tin, or a combination thereof wherein “n” is an integer equalto or greater than 0; wherein each R₁ independently comprises a straightchain alkyl group, a branched alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an alkoxy group, an aryloxy group,heterocyclic group, a monocyclic aromatic group, a polycyclic aromaticgroup, an aryl, an alkylaryl group, an arylalkyl group, an akylenegroup, a hydrogen, a halogen, or a combination thereof and wherein R₂comprises an aryl containing group comprising from greater than or equalto about 6 to about 22 carbon atoms, wherein the aryl containing groupcan optionally be substituted at any one or more positions by one ormore heteroatoms, wherein the heteroatom, if present, can comprise ahalogen, oxygen, sulfur, nitrogen, or a combination thereof.

In a further aspect, a photovoltaic cell is disclosed, wherein aphotoactive region comprises a small molecule organic semiconductorcomprising an aryloxy-phtalocyanine of group IV metals comprising acompound of a general formula (II):

wherein M is one or more group IV metals and comprises silicon,germanium, tin, or a combination thereof wherein “n” is an integer equalto or greater than 0; wherein each R₁ independently comprises a straightchain alkyl group, a branched alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an alkoxy group, an aryloxy group,heterocyclic group, a monocyclic aromatic group, a polycyclic aromaticgroup, an aryl group, an alkylaryl group, an arylalkyl group, an akylenegroup, a hydrogen, a halogen, or a combination thereof and wherein R₂and R₃ are the same or different and can independently comprise ahalogen, oxygen, sulfur, nitrogen, aryl or an aryloxy containing groupcomprising from greater than or equal to about 6 to about 22 carbonatoms, wherein the aryl containing group can optionally be substitutedat any one or more positions by one or more of heteroatoms, wherein theheteroatom, if present, can comprise a halogen, oxygen, sulfur,nitrogen, or a combination thereof.

In yet another aspect, a method for preparing a photovoltaic cellcomprising an aryloxy-phthalocyanine of group IV metals is disclosed.

Additional advantages will be set forth in part in the description whichfollows, and in part will be obvious from the description, or can belearned by practice of the aspects described below. The advantagesdescribed below will be realized and attained by means of the elementsand combinations particularly pointed out in the appended claims. It isto be understood that both the foregoing general description and thefollowing detailed description are exemplary and explanatory only andare not restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate several aspects described below.Like numbers represent the same elements throughout the figures.

FIG. 1 illustrates UV-VIS absorbance of (m-cresol)₂-SiPc,(m-cresol)₂-GePc and (PDP)₂—SnPc, in accordance with various aspects ofthe present disclosure.

FIG. 2 Illustrates cyclic voltammograms of (m-cresol)₂-SiPc,(m-cresol)₂-GePc and (PDP)₂—SnPc, in accordance with various aspects ofthe present disclosure.

DETAILED DESCRIPTION

In one aspect, described herein are compounds of a general structure(I):

wherein M comprises silicon, germanium, tin, or a combination thereof;wherein “n” is an integer equal to or greater than 0; wherein each R₁comprises a straight chain alkyl group, a branched alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group,an aryloxy group, heterocyclic group, a monocyclic aromatic group, apolycyclic aromatic group, an aryl group, an alkylaryl group, anarylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ comprises an optionally substitutedaryl containing group comprising from greater than or equal to about 6to about 22 carbon atoms, wherein the aryl containing group, ifsubstituted, can be substituted at one or more positions by one or moreof the same or different heteroatoms comprising a halogen, oxygen,sulfur, nitrogen, or a combination thereof.

In one aspect, “n” ranges from about 0 to about 4.

In one aspect, R₂ comprises an optionally substituted aryl containinggroup comprising from greater than or equal to about 6 to about 18carbon atoms, or from greater than or equal to about 6 to about 10carbon atoms and wherein not all of which are considered aromatic carbonatoms, wherein, the aryl containing group, if substituted, can besubstituted at one or more positions by one or more of the same ofdifferent heteroatoms comprising a halogen, oxygen, sulfur, nitrogen, ora combination thereof.

In another aspect, R₂ does not comprise a metal.

In another aspect, R₂ does not comprise a heteroatom as a bridginggroup.

In another aspect, R₁ and R₂ are the same or different and at least oneof R₁ and R₂ can comprise a hydrocarbon, hydrogen, halogen such as, forexample, bromine, chlorine, fluorine, or iodine, or a combinationthereof.

In yet another aspect, R₁ and R₂ are the same or different and at leastone of R₁ and R₂ can comprise a C₁-C₂₀-alkyl group: straight-chain orbranched hydrocarbon radicals having up to about 20 carbon atoms, forexample C₁-C₁₀-alkyl or C₁₁-C₂₀-alkyl, or a C₁-C₁₀-alkyl, for exampleC₁-C₃-alkyl, such as methyl, ethyl, propyl, isopropyl, or C₄-C₆-alkyl,n-butyl, sec-butyl, tert-butyl, 1,1-dimethylethyl, pentyl,2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl,3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, or C₇-C₁₀-alkyl such as heptyl, octyl,2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl ordecyl, and/or isomers or combinations thereof.

In another aspect, R₁ and R₂ are the same or different and at least oneof R₁ and R₂ can comprise a C₂-C₂₀-alkenyl group: unsaturated,straight-chain or branched hydrocarbon radicals having from about 2 toabout 20 carbon atoms and a double bond in any position, for exampleC₂-C₁₀-alkenyl or C₁₁-C₂₀-alkenyl, a C₂-C₁₀-alkenyl such asC₂-C₄-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, orC₅-C₆-alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, and alsoC₇-C₁₀-alkenyl such as the isomers of heptenyl, octenyl, nonenyl,decenyl, or a combination thereof.

In yet another aspect, R₁ and R₂ are the same or different and at leastone of R₁ and R₂ can comprise a C₂-C₂₀-alkynyl group: straight-chain orbranched hydrocarbon groups having from about 2 to about 20 carbon atomsand a triple bond in any position, for example C₂-C₁₀-alkynyl orC₁₁-C₂₀-alkynyl, a C₂-C₁₀-alkynyl such as C₂-C₄-alkynyl, such asethynyl, 1-propynyl, 2-propynyl, 1-butyryl, 2-butyryl, 3-butyryl,1-methyl-2-propynyl, or C₅-C₇-alkynyl, such as 1-pentynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-2-butyryl, 1-methyl-3-butyryl,2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl,1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl,4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butyryl, 3,3-dimethyl-1-butynyl,1-ethyl-2-butynyl, 1-ethyl-3-butyryl, 2-ethyl-3-butyryl or1-ethyl-1-methyl-2-propynyl, and C₇-C₁₀-alkynyl such as the isomers ofheptynyl, octynyl, nonynyl, decynyl, or a combination thereof.

In another aspect, R₁ and R₂ are the same or different and at least oneof R₁ and R₂ can comprise a C₃-C₁₈-cycloalkyl group: monocyclicsaturated hydrocarbon groups having from about 3 up to about 18 carbonring members, or a C₃-C₈-cycloalkyl such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, and a saturated orunsaturated cyclic system, for example norbornyl or norbenzyl. In yetanother aspect, R₁ and R₂ can be substituted with groups independentlyselected from all possible isomers and enantiomers, including mixturesof isomers or enantiomers.

In another aspect, R₁ and R₂ are the same or different and at least oneof R₁ and R₂ can comprise a heterocycle, for example, five- totwelve-member, five- to nine-member, five- to six-member, ring systemshaving oxygen, nitrogen and/or sulfur atoms and optionally a pluralityof rings, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl,benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl,dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl,dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenylor tert-butylthiophenyl. Moreover, R₁ and/or R₂ can comprise a five- orsix-member saturated nitrogen-containing ring systems attached via aring nitrogen atom and which can comprise one or two further nitrogenatoms or a further oxygen or sulfur atom. In another aspect, R₁ and R₂can comprise C₂-C₁₇ Heterocycloalkyl, for example, aziridinyl, oxiranyl,thiiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl,tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl,tetrahydro-2H-pyranyl, tetrahydro-2H-thiopyranyl, azepanyl, oxepanyl,thiepanyl, azocanyl, oxocanyl, thiocanyl, imidazolidinyl, pyrazolidinyl,oxazolidinyl, piperazinyl, tetrahydropyrimidinyl, tetrahydropyridazinyl,oxazinanyl, morpholinyl, diazepanyl, thiomorpholinyl,pyrrolo[3,4-c]pyrrolyl, or combinations thereof.

In one aspect, R₁ comprises a C₁-C₂₀-alkoxy group: a straight-chain orbranched alkyl group having from about 1 to about 20 carbon atoms (asspecified above) which is attached via an oxygen atom (—O—), for exampleC₁-C₁₀-alkoxy or C₁₁-C₂₀-alkoxy, a C₁-C₁₀-alkyloxy, or a C₁-C₃-alkoxy,for example methoxy, ethoxy, propoxy.

In another aspect, R₁ comprises an aryloxy containing group, forexample, a mono- to tricyclic aromatic ring system (as described above)which is attached via an oxygen atom (—O—), or a mono- to bicyclic, or amonocyclic, aromatic ring system.

In another aspect, R₁ and R₂ are the same or different and at least oneof R₁ and R₂ can comprise an arylalkyl group, for example, a mono- totricyclic aromatic ring system (as specified above) which is attachedvia a C₁-C₂₀-alkylene group, a mono- to bicyclic, or a monocyclic,aromatic ring system.

In another aspect, R₁ and/or R₂ comprise a C₁-C₂₀-alkylene group, forexample, a straight-chain or branched hydrocarbon radicals having fromabout 1 to about 20 carbon atoms, for example C₁-C₁₀-alkylene orC₁₁-C₂₀-alkylene, C₂-C₁₀-alkylene, such as, for example, methylene,dimethylene, trimethylene, tetramethylene, pentamethylene orhexamethylene.

In another aspect, R₁ and/or R₂ comprises an aryl group, for example, amono- to tricyclic aromatic ring system comprising from greater than orequal to about 6 to about 22 carbon ring members, for example phenyl,naphthyl or anthracenyl, a mono- to bicyclic, or a monocyclic, aromaticring system.

In yet another aspect, R₂ comprises a mono- to tricyclic aromatic ringsystem comprising from greater than or equal to about 6 to about 22carbon ring members, greater than or equal to about 6 and about 18carbon ring members, or from greater than or equal to about 6 to about10 carbon ring members, wherein not all carbons are necessarilyaromatic, and wherein the ring system can optionally be substituted atany one or more positions by one or more heteroatoms. In another aspect,such a heteroatom can comprise a halogen, oxygen, sulfur, nitrogen, or acombination thereof. In a further aspect, a heteroatom, if present, cancomprise a chlorine, fluorine, bromine, iodine, or a combinationthereof.

In one aspect, R₂ comprises a mono-to tricyclic aromatic ring systemcomprising from greater than or equal to about 6 to about 22 carbon ringmembers, greater than or equal to about 6 and about 18 carbon ringmembers, greater than or equal to about 6 to about 10 carbon ringmembers, wherein not all carbons are necessarily aromatic, and whereinthe ring system can optionally be substituted at any one or morepositions by one or more halogens. In one aspect, a halogen does notcomprise chlorine. In a further aspect, a halogen comprises fluorine,chlorine bromine, iodine, or a combination thereof. In a yet furtheraspect, wherein a single chlorine is present on a given ring system, thering system is not substituted in a para-position. In a yet even furtheraspect, wherein a halogen comprises chlorine, the ring system issubstituted at one or more ortho-positions. While not wishing to bebound to a particular theory, it is believed that the substituted R₂ canbe highly electronegative so as to affect the electron cloud around themetal.

In another aspect, any of the hydrocarbon groups can be optionallysubstituted one, two, or more times at any position with the same ordifferent substituting moiety such as a nitrogen containing group, forexample, amino and/or nitro; a sulfur containing group, for example,thiol, sulfoxide, sulfate, and/or chlorosulfate; a hydroxyl group; asilicon containing group, for example, a trisubstituted silane where thesubstituent is a hydrocarbon; a halogen, for example, bromine, chlorine,fluorine, and/or iodine; and a hetero atom moiety, having for exampleabout 3 to about 15 atoms, and including an element selected forinstance from the group consisting of nitrogen, sulfur, silicon, andoxygen, such as thiophen-2-yl, thiophen-3-yl, pyridine-2-yl,pyridine-3-yl, pyridine-4-yl, furna-2-yll, furan-3-yl, and the like.Exemplary substituted hydrocarbon groups include for instance thefollowing: 3-hydroxyhenan-1,6,-dyyl; 2-methyl-benzen-1,4,-diyl; and2,5-dimethylbenzen-1,4,diyl.

In yet another aspect, the present disclosure provides a compound havingthe general structure (II):

wherein M comprises silicon, germanium, tin, or a combination thereof,wherein “n” is an integer equal to or greater than 0; wherein each R₁comprises a straight chain alkyl group, a branched alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group,an aryloxy group, heterocyclic group, a monocyclic aromatic group, apolycyclic aromatic group, an aryl group, an alkylaryl group, anarylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ and R₃ are the same or different andcomprise a halogen, oxygen, sulfur, nitrogen, aryl or an optionallysubstituted aryloxy containing group comprising from greater than orequal to about 6 to about 22 carbon atoms, wherein if present andsubstituted, an aryloxy containing group can be substituted in one ormore positions by one or more of the same of different heteroatomscomprising a halogen, oxygen, sulfur, nitrogen, or a combinationthereof.

In one aspect, “n” can range from about 0 to about 4.

In another aspect, R₁, R₂, and R₃ can be the same or different and cancomprise a hydrocarbon; hydrogen; halogen, such as bromine, chlorine,fluorine, and iodine; or a combination thereof.

In at least one aspect, R₂ and R₃ are the same or different and at leastone of R₂ and R₃ can comprise an optionally substituted aryloxycontaining group comprising from greater than or equal to about 6 toabout 18 carbon atoms, or from greater than 6 to about 10 carbon atoms,wherein if substituted, can be substituted at one or more positions byone or more heteroatoms comprising a halogen, oxygen, sulfur, nitrogen,or a combination thereof.

In yet another aspect, R₂ and R₃ do not comprise a metal.

In yet another aspect, R₂ and R₃ do not comprise a heteroatom as abridging group.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise a C₁-C₂₀-alkyl group: straight-chain orbranched hydrocarbon radicals having up to about 20 carbon atoms, forexample C₁-C₁₀-alkyl or C₁₁-C₂₀-alkyl, a C₁-C₁₀-alkyl, for exampleC₁-C₃-alkyl, such as methyl, ethyl, propyl, isopropyl, or C₄-C₆-alkyl,n-butyl, sec-butyl, tert-butyl, 1,1-dimethylethyl, pentyl,2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl,3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, or C₇-C₁₀-alkyl such as heptyl, octyl,2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl ordecyl, and isomers thereof.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise a C₂-C₂₀-alkenyl group: unsaturated,straight-chain or branched hydrocarbon radicals having from about 2 toabout 20 carbon atoms and a double bond in any position, for exampleC₂-C₁₀-alkenyl or C₁₁-C₂₀-alkenyl, a C₂-C₁₀-alkenyl such asC₂-C₄-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, orC₅-C₆-alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hex enyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, and alsoC₇-C₁₀-alkenyl such as the isomers of heptenyl, octenyl, nonenyl ordecenyl.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise a C₂-C₂₀-alkynyl group: straight-chain orbranched hydrocarbon groups having from about 2 to about 20 carbon atomsand a triple bond in any position, for example C₂-C₁₀-alkynyl orC₁₁-C₂₀-alkynyl, a C₂-C₁₀-alkynyl such as C₂-C₄-alkynyl, such asethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, or C₅-C₇-alkynyl, such as 1-pentynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl,2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl,1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl,4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl,1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl or1-ethyl-1-methyl-2-propynyl, and C₇-C₁₀-alkynyl such as the isomers ofheptynyl, octynyl, nonynyl, decynyl.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise a C₃-C₁₈-cycloalkyl group, for example,monocyclic saturated hydrocarbon groups having from about 3 up to about18 carbon ring members, a C₃-C₈-cycloalkyl such as cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, and asaturated or unsaturated cyclic system, for example norbornyl ornorbenzyl. In yet another aspect, R₁ and R₂ can be substituted withgroups independently selected from other isomers and enantiomers,including mixtures of isomers or enantiomers, that one of ordinary skillin the art would deem appropriate.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise a heterocycle, for example, five- totwelve-member, five- to nine-member, five-to six-member, ring systemshaving oxygen, nitrogen and/or sulfur atoms and optionally a pluralityof rings, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl,benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl,dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl,dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenylor tert-butylthiophenyl; or moreover, five- or six-member saturatednitrogen-containing ring systems which are attached via a ring nitrogenatom and which can also comprise one or two further nitrogen atoms or afurther oxygen or sulfur atom.

In another aspect, R₁, R₂, and/or R₃ can comprise a C₂-C₁₇heterocycloalkyl, for example, aziridinyl, oxiranyl, thiiranyl,azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, tetrahydrofuranyl,tetrahydrothiophenyl, piperidinyl, tetrahydro-2H-pyranyl,tetrahydro-2H-thiopyranyl, azepanyl, oxepanyl, thiepanyl, azocanyl,oxocanyl, thiocanyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl,piperazinyl, tetrahydropyrimidinyl, tetrahydropyridazinyl, oxazinanyl,morpholinyl, diazepanyl, thiomorpholinyl, pyrrolo[3,4-c]pyrrolyl, or acombination thereof.

In another aspect, R₁, R₂, and R₃ are the same or different and can atleast one of R₁, R₂, and R₃ comprise a C₁-C₂₂-alkoxy group: astraight-chain or branched alkyl group having from about 1 to about 22carbon atoms (as specified above) which is attached via an oxygen atom(—O—), for example C₁-C₁₀-alkoxy or C₁₁-C₂₀-alkoxy, a C₁-C₁₀-alkyloxy,or a C₁-C₃-alkoxy, for example methoxy, ethoxy, propoxy.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ can comprise an aryloxy containing group, forexample, a mono- to tricyclic aromatic ring system (as specified above)which is attached via an oxygen atom (—O—), a a mono- to bicyclic, or amonocyclic, aromatic ring system.

In another aspect, R₁, R₂, and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise an arylalkyl containing group, forexample, a mono- to tricyclic aromatic ring system (as specified above)which is attached via a C₁-C₂₀-alkylene group, a mono- to bicyclic, or amonocyclic, aromatic ring system.

In another aspect, R₁, R₂ and R₃ are the same or different and at leastone of R₁, R₂, and R₃ comprise a C₁-C₂₀-alkylene containing group, forexample, straight-chain or branched hydrocarbon radicals having fromabout 1 to about 20 carbon atoms, for example C₁-C₁₀-alkylene orC₁₁-C₂₀-alkylene, or a C₂-C₁₀-alkylene, especially methylene,dimethylene, trimethylene, tetramethylene, pentamethylene orhexamethylene.

In another aspect, R₁, R₂ and R₃ are the same or different and at leastone of R₁, R₂, and R₃ can comprise an aryl containing group, forexample, a mono- to tricyclic aromatic ring system comprising greaterthan or equal to about 6 to about 22 carbon ring members, for examplephenyl, naphthyl or anthracenyl, a mono- to bicyclic, or a monocyclic,aromatic ring system.

In another aspect, R₂ and R₃ are the same or different and can comprisea mono- to tricyclic aromatic ring system comprising from greater thanor equal to about 6 to about 22 carbon ring members, from greater thanor equal to about 6 and about 18 carbon ring members, or from greaterthan or equal to about 6 and about 10 carbon ring members, wherein notall carbon atoms are necessarily aromatic, and wherein the ring systemcan be optionally substituted at any one or more positions by one ormore of the same of different heteroatoms, such as, for example, ahalogen, oxygen, sulfur, nitrogen, or a combination thereof. In afurther aspect, a heteroatom, if present, can comprise chlorine,fluorine, bromine, iodine, or a combination thereof.

In one aspect, R₂ and R₃ are the same or different and can comprise amono-to tricyclic aromatic ring system comprising from greater than orequal to about 6 to about 22 carbon ring members, greater than or equalto about 6 and about 18 carbon ring members, greater than or equal toabout 6 to about 10 carbon ring members, wherein not all carbons arenecessarily aromatic, and wherein the ring system can optionally besubstituted at any one or more positions by one or more halogens. In oneaspect, a halogen does not comprise chlorine. In a further aspect, ahalogen comprises fluorine, chlorine bromine, iodine, or a combinationthereof. In a yet further aspect, wherein a single chlorine is presentin a given ring system, the ring system is not substituted in apara-position. In a yet even further aspect, wherein a halogen compriseschlorine, the ring system is substituted at one or more ortho-positions.While not wishing to be bound to a particular theory, it is believedthat the substituted R₂ can be highly electronegative so as to affectthe electron cloud around the metal.

In another aspect, any of the hydrocarbon groups described herein can beoptionally substituted at one, two, or more positions with the same ordifferent substituting moiety such as, for example, a nitrogencontaining groups such as amino and nitro; a sulfur containing groupsuch as thiol, sulfoxide, sulfate, chlorosulfate; a hydroxyl group; asilicon containing group such as a trisubstituted silane where thesubstituent is a hydrocarbon; a halogen such as bromine, chlorine,fluorine, and iodine; and a hetero atom moiety, having for example 3 to15 atoms, and including an element selected for instance from the groupconsisting of nitrogen, sulfur, silicon, and oxygen, such asthiophen-2-yl, thiophen-3-yl, pyridine-2-yl, pyridine-3-yl,pyridine-4-yl, furna-2-yll, furan-3-yl, and the like. Exemplarysubstituted hydrocarbon groups include for instance the following:3-hydroxyhenan-1,6,-dyyl; 2-methyl-benzen-1,4,-diyl; and2,5-dimethylbenzen-1,4,diyl.

In another aspect, R₂ and R₃ are the same or different and comprise ahalogen, oxygen, sulfur, nitrogen, or a combination thereof.

A. Synthetic Methods

Described herein are methods for making a compound having the generalstructure described herein. In one aspect, the method for preparing thecompounds described herein can comprise: (a) providing a compoundcomprising a halogen-metal bond containing R₁ substituted phthalocyanineprecursor, wherein the halogen comprises chlorine, bromine, iodine,fluorine, or a combination thereof, and each R₁ comprises a straightchain alkyl group, a branched alkyl group, a cycloalkyl group, analkenyl group, an alkynyl group, an alkoxy group, an aryloxy group,heterocyclic group, a monocyclic aromatic group, a polycyclic aromaticgroup, an aryl group, an alkylaryl group, an arylalkyl group, an akylenegroup, a hydrogen, a halogen, or a combination thereof; (b) providing areactant comprising an optionally substituted aryl (—R₂) and/oroptionally-substituted arylalcohol group (OH—R₂), wherein R₂ comprisesfrom greater than or equal to about 6 to about 22 carbon atoms, andwherein not all of the carbon atoms are necessarily aromatic, and ifsubstituted, can be substituted at any one or more positions by one ormore heteroatoms, such as, for example, a halogen, oxygen, sulfur,nitrogen, or a combination thereof, and (c) reacting the compoundcomprising a halogen-metal bond containing phthalocyanines precursor andthe reactant in the presence of an organic solvent under conditionseffective to form the compound of the general structure (I), wherein thecompound of the general structure (I) is non-soluble, negligiblysoluble, partially soluble in an organic solvent, or at least partiallysoluble in an organic solvent.

The preparation of metal-free phthalocyanines (PC) is known in the art.For example, U.S. Pat. No. 3,509,146 describes the preparation ofmetal-free phthalocyanines (Pc) and related compounds by mixing1,3-diiminoisoindolines or their heterocyclic analogs withalkylalanolamines. EP 0 373 643 A2 describes the preparation of metalcontaining phthalocyanines, for example, the synthesis of metalcontaining phthalocyanines by reaction of mixtures ofo-phthalodinitriles and/or 1,30 diiminoisoindolines with metalliccompounds. Furthermore, M. Durmus et al., Tetrahedron, 2007, 1385describe preparation of halogen-metal bond containing phthalocyanines.These compounds can be prepared for example, by the treatment ofphthalonitriles with a metal chloride in freshly distilled quinolinesolvent.

In one aspect, step (b) of the method for preparing compounds having thegeneral structure (I) comprises providing a reactant comprising anoptionally substituted aryl (—R₂) and/or an optionally substitutedarylalcohol groups (OH—R₂), wherein R₂ comprises from greater than orequal to about 6 to about 18 carbon atoms, or from greater than or equalto about 6 to about 10 carbon atoms, wherein not all of the carbon atomsare necessarily aromatic, and wherein, if substituted, the reactant canbe substituted at one or more positions by one or more heteroatoms, forexample, comprising a halogen, oxygen, sulfur, nitrogen, or acombination thereof.

In another aspect, step (b) of the method for preparing a compoundhaving the general structure (I) comprises providing a reactantcomprising an optionally substituted aryl (—R₂) and/or an optionallysubstituted arylalcohol groups (OH—R₂), wherein R₂ comprises a mono- totricyclic aromatic ring system comprising from greater than or equal toabout 6 to about 22 carbon ring members, greater than or equal to about6 and about 18 carbon ring members, or from greater than or equal toabout 6 to about 10 carbon ring members, wherein not all carbons arenecessarily aromatic, and wherein the ring system can optionally besubstituted at any one or more positions by one or more heteroatoms. Ina further aspect, such a heteroatom can comprise a halogen, oxygen,sulfur, nitrogen or a combination thereof. In a yet further aspect, aheteroatom, if present, can comprise a chlorine, fluorine, bromine,iodine, or a combination thereof.

In one aspect, step (b) of the method for preparing a compound havingthe general structure (I) comprises providing a reactant comprising anoptionally substituted aryl (—R₂) and/or an optionally substitutedarylalcohol groups (OH—R₂), wherein R₂ comprises a mono- to tricyclicaromatic ring system comprising from greater than or equal to about 6 toabout 22 carbon ring members, greater than or equal to about 6 and about18 carbon ring members, or from greater than or equal to about 6 toabout 10 carbon ring members, wherein not all carbons are necessarilyaromatic, and wherein the ring system can optionally be substituted atany one or more positions by one or more halogens. In one aspect, ahalogen does not comprise chlorine. In a further aspect, a halogen cancomprise a chlorine, fluorine, bromine, iodine, or a combinationthereof. In a yet further aspect, wherein a halogen comprises chlorine,the ring system is not substituted in a para-position. In a yet evenfurther aspect, wherein a halogen comprises chlorine, the ring system issubstituted at one or more ortho-positions. While not wishing to bebound to a particular theory, it is believed that the substituted R₂ canbe highly electronegative so as to the affect electron cloud around themetal.

In another aspect, a method for preparing a compound of the generalmolecular structure (II) comprises the steps of: (a) providing acompound comprising a halogen-metal bond containing R₁ substitutedphthalocyanine precursor, wherein the halogen comprises chlorine,bromine, iodine, fluorine, or a combination thereof, and wherein andeach R₁ can independently comprise a straight chain alkyl group, abranched alkyl group, a cycloalkyl group, an alkenyl group, an alkynylgroup, an alkoxy group, an aryloxy group, heterocyclic group, amonocyclic aromatic group, a polycyclic aromatic group, an alkylarylgroup, an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; (b) providing a reactant comprising R₂ and/or R₃moieties, wherein R₂ and/or R₃ are the same or different and cancomprise an optionally substituted aryloxy group comprising from greaterthan or equal to about 6 to about 22 carbon atoms, wherein not all ofthe carbon atoms are necessarily aromatic, and wherein if substituted,can be substituted at any one or more positions with one or moreheteroatoms, such as, for example, a halogen, oxygen, sulfur, nitrogen,or a combination thereof, and (c) reacting the compound comprising ahalogen-metal bond containing phthalocyanine precursor and the reactantin the presence of an organic solvent under conditions effective to formthe compound of the general structure (II), wherein the compound of thegeneral structure (II) is non-soluble, negligibly soluble, partiallysoluble in an organic solvent, or at least partially soluble in anorganic solvent. In yet another aspect, upon conditions effective toform the compound of the general structure (II), compounds comprising R₂and/or R₃ moieties are added simultaneously or in number of steps.

In yet a further aspect, R₂ and R₃ are the same or different and canindependently comprise an optionally substituted aryloxy containinggroup comprising from greater than or equal to about 6 to about 18carbon atoms, or from greater than or equal to about 6 to about 10carbon atoms, wherein not all carbon atoms are necessarily aromatic, andwherein, if substituted, can be substituted at any one or more positionsby one or more of the same or different heteroatoms, such as, forexample, a halogen, oxygen, sulfur, nitrogen, or a combination thereof.

In another aspect, step (b) of the method for preparing a compoundhaving the general structure (II) comprises providing a reactantcomprising an optionally substituted aryl (—R₂) or (—R₃) and/or anoptionally substituted arylalcohol groups (OH—R₂) or (OH—R₃), wherein R₂and R₃ are the same or different and can comprise a mono- to tricyclicaromatic ring system comprising from greater than or equal to about 6 toabout 22 carbon ring members, greater than or equal to about 6 and about18 carbon ring members, or from greater than or equal to about 6 toabout 10 carbon ring members, wherein not all carbons are necessarilyaromatic, and wherein the ring system can optionally be substituted atany one or more positions by one or more heteroatoms. In a furtheraspect, such a heteroatom can comprise a halogen, oxygen, sulfur,nitrogen or a combination thereof. In a yet further aspect, aheteroatom, if present, can comprise a chlorine, fluorine, bromine,iodine, or a combination thereof.

In one aspect, step (b) of the method for preparing a compound havingthe general structure (II) comprises providing a reactant comprising anoptionally substituted aryl (—R₂) or (—R₃) and/or an optionallysubstituted arylalcohol groups (OH—R₂) or (OH—R₃), wherein R₂ and R₃ arethe same or different and can comprise a mono- to tricyclic aromaticring system comprising from greater than or equal to about 6 to about 22carbon ring members, greater than or equal to about 6 and about 18carbon ring members, or from greater than or equal to about 6 to about10 carbon ring members, wherein not all carbons are necessarilyaromatic, and wherein the ring system can optionally be substituted atany one or more positions by one or more halogens. In one aspect, ahalogen does not comprise chlorine. In a further aspect, a halogen cancomprise a chlorine, fluorine, bromine, iodine, or a combinationthereof. In a yet further aspect, wherein a halogen comprises chlorine,the ring system is not substituted in a para-position. In a yet evenfurther aspect, wherein a halogen comprises chlorine, the ring system issubstituted at one or more ortho-positions.

In another aspect, the compounds of the general structure (I) and/or(II) can be prepared in the presence of a solvent. In one aspect,suitable solvents can comprise substances which are liquid at thetemperatures of the process according to the invention and in which allcompounds involved are at least partly soluble. For example, suchsolvents have boiling points of over about 100° C. at standard pressure(101.325 kPa). The solutions of the compounds of the general structure(I) and/or (II) used in the method according to the invention in thepresence of a solvent can also have the properties of suspensions ordispersions. Suitable solvents can comprise, for example, aromaticcompounds or polar aprotic compounds. In one aspect, the solvent cancomprise toluene, xylene, mesitylene, teralin, chlorobenzene,dichlorobenzene, quinoline, pyridine, sulfolane, THF, chloromethane,chloroform, dimethyl sulfoxide, or a combination thereof. The amount ofsolvent which can be used in the process according to the invention isdependent upon the solubility of the compounds dissolved and cantherefore vary within a wide range. In another aspect, one or moresolvents can be added in excess (weight ratio).

In one aspect, the temperatures which are established for thepreparation of the general compounds of the structure (I) and (II) inthe method according to the invention can vary within a wide range. Ingeneral, the selection of the temperature can, for example, depend onthe solubility of one or more compounds involved to form the compoundsof the of the general structure (I) and (II), and can be determined byone of ordinary skill in the art. In one aspect, wherein solubility ishigh, it can be possible, for example, to select relatively lowtemperatures for the reaction in the method according to the invention.The temperatures in the method according to the invention can generallybe selected from the range of from about 0° C. to about 200° C. Inanother aspect, the temperature can be in the range of from about 20° C.to about 150° C. In another aspect, the temperature can be in the rangeof from about 70° C. to about 140° C.

In another aspect, the pressure range within which the method accordingto the invention for preparing compounds of the general structure (I)and (II) are performed can vary. In various aspects, the methodaccording to the invention can be performed at standard pressure,slightly reduced pressure or else elevated pressure. In one aspect, thepressure can be selected from the range of from about 90 kPa to about1000 kPa.

The process can be performed in any apparatus which is suitable for thispurpose, such as, for example, those known to one skilled in the art oforganic compounds. For the removal and workup of the compounds ofgeneral molecular structure (I) and (II), it is possible to use anymethods with which the person skilled in the art is familiar. Forexample, the removal can be performed by, for example, filtration orphase separation. In another aspect, the workup can comprise apurification step, such as, for example, washing the compounds with aliquid, and/or a drying step.

In another aspect, the duration of all time steps (a) to (c) overall,and also of any individual step, can vary, for example, depending on thetemperature. In another aspect, the duration of all time steps togethercan vary within a wide range from a few minutes up to, for example,about 72 hours.

It should be understood that the methods described herein are intendedto be exemplary and are not intended to be limiting. Other methods canbe used to prepare the inventive compositions described herein, and thepresent invention is not intended to be limited to the specific methodsrecited herein.

B. Solar Cells

As used herein, a first “Highest Occupied Molecular Orbital” (HOMO) or“Lowest Unoccupied Molecular Orbital (LUMO) energy level is “greaterthan” or “higher than” a second HOMO or LUMO energy level if the firstenergy level is closer to the vacuum energy level. Since ionizationpotentials (IP) are measured as a negative energy relative to a vacuumlevel, a higher HOMO energy level corresponds to an IP having a smallerabsolute value (an IP that is less negative). Similarly, a higher LUMOenergy level corresponds to an electron affinity (EA) having a smallerabsolute value (an EA that is less negative). On a conventional energylevel diagram, with the vacuum level at the top, the LUMO energy levelof a material is higher than HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

In the context of organic materials, the terms “donor” and “acceptor”refer to relative positions of the HOMO and LUMO energy levels of twocontacting but different organic materials. The term “electron donor”refers to the material's electron affinity. An electron donor materialhas a relative low electron affinity, i.e. the EA value has a smallerabsolute value. As such, an electron donor material tends to act asp-type material. In other words, an electron donor material can act as ahole transport material. The term “electron acceptor” refers tomaterial's electron affinity. An electron acceptor material has arelatively high electron affinity. As such, an electron acceptormaterial can act as an electron transport material.

The term “charge transport material” as used herein refers to a materialtransports charge, i.e. holes or electrons. An electron donor materialtransports holes and an electron acceptor material transports electrons.

The term “photoactive region” as used herein is a portion of aphotosensitive device that absorbs electromagnetic radiation to generateexcitation (i.e. electrically neutral excited state in form ofelectron-hole pairs).

Described herein are uses of compounds having the general molecularstructures (I) and (II). In one aspect, photovoltaic cells comprisingcompounds having the general molecular structure (I) and (II) aredescribed.

In one aspect, a photovoltaic cell comprising a compound having thegeneral molecular structure (I):

wherein M comprises silicon, germanium, tin, or a combination thereof;wherein “n” is an integer equal to or greater than 0; wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ comprises an optionally substitutedaryl containing group comprising from greater than or equal to about 6to about 22 carbon atoms, wherein aryl containing group, if substituted,can be substituted at one or more positions with one or more of the sameor different heteroatoms comprising a halogen, oxygen, sulfur, nitrogen,or a combination thereof.

In another aspect, a photovoltaic cell comprising a compound having thegeneral molecular structure (II):

wherein M comprises silicon, germanium, tin, or a combination thereof,wherein “n” is an integer equal to or greater than 0; wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an alkylaryl group, an arylalkylgroup, an akylene group, a hydrogen, a halogen, or a combinationthereof; and wherein R₂ and R₃ are the same or different and comprise ahalogen, oxygen, sulfur, nitrogen, aryl or an optionally substitutedaryloxy containing group comprising from greater than or equal to about6 to about 22 carbon atoms, wherein aryl containing group, ifsubstituted, can be substituted at one or more positions with one ormore of the same or different heteroatoms comprising a halogen, oxygen,sulfur, nitrogen, or a combination thereof.

In one aspect, no reports of phenoxy substituted group III metalcontaining phthalocyanines are known for the fabrication of organicphotovoltaic devices.

Organic solar cells generally have a layered structure and generallycomprise at least the following layers: anode, photoactive region, andcathode. These layers are generally disposed on a substrate. Thestructure of organic solar cells can vary, and various structures areknown in the art, for example, in US 2005/0098726 and US 2005/0224905,which are fully incorporated here by reference.

Organic solar cells make use of heterogeneous junction regions ofconjugated hole- and electron-conducting molecules to produce separatedelectrical charges after photo-induced charge transfer from theelectron-donor to the electron-acceptor component.

In one aspect, the invention provides an organic solar cell comprising asubstrate with at least one cathode, at least one anode, and at leastone compound of the general molecular structure (I) and/or (II) asdefined above as a photoactive material. In another aspect, the organicsolar cell according to the invention comprises at least one photoactiveregion. A photoactive region can comprise two layers that each has ahomogeneous composition and form a planar donor-acceptor heterojunction(PHJ) or a mixed layer forming a donor-acceptor bulk heterojunction(BHJ).

In organic semiconductors, light absorption leads to the creation ofexcitations, (i.e. electron-hole pairs) through promotion of an electronfrom the HOMO to the LUMO level of the molecules. In order to produceseparated charges, the excitations can be dissociated at thedonor-acceptor interface, the driving force for this process beingprovided by the energy offset between the LUMO orbitals of the donor andacceptor molecules.

Consequently, the four basic steps occurring in a molecular baseddevice: (a) light absorption/excitation generation; (b) excitationdiffusion towards the donor-acceptor junction; (c) chargetransfer/excitation dissociation; and (d) charge collection of theseparated electrons and holes at the external electrodes.

The performance of the cells is usually determined by the analysis ofthe current-voltage (I-V) curves, from which key parameters such as theopen-circuit (V_(OC)) (associated to the gap between the LUMO level ofthe acceptor and the HOMO level of the donor), short-circuit density(J_(SC)) (proportional to how much light can be absorbed), fill factor(FF) and power conversion efficiency (PCE) are extracted.

Suitable substrates for organic solar cells can comprise, for example,materials such as glass, ceramic, SiO₂, quartz, polymers such aspolyvinyl chloride, polyolefins such as polyethylene and polypropylene,polyesters, fluoropolymers, polyamides, polyurethanes,polyalkyl(meth)acrylates, polystyrene and mixtures and compositesthereof and combinations thereof.

Suitable electrodes (cathode and anode) can comprise metals (forexample, of groups 8, 9, 10 or 11 of the Periodic Table, e.g. Pt, Au,Ag, Cu, Al, In, Mg, Ca), semiconductors (e.g. doped Si, doped Ge, indiumtin oxide (ITO), gallium indium tin oxide (GITO), zinc indium tin oxide(ZITO), etc.), metal alloys (e.g. based on Pt, Au, Ag, Cu, etc.,especially Mg/Ag alloys), semiconductor alloys, etc. One of theelectrodes used can be a material essentially transparent to incidentlight. This includes, for example, ITO, doped ITO, FTO (fluorine dopedtin oxide), AZO (aluminium doped ZnO), ZnO, TiO₂, Ag, Au, Pt. The otherelectrode used can be a material which essentially reflects the incidentlight. This includes, for example, metal films, for example of Al, Ag,Au, In, Mg, Mg/Al, Ca, etc.

For its part, the photoactive region can comprise at least one layerwhich comprises, as an organic semiconductor material, at least onecompound of the general molecular structure (I) or (II) as definedabove. In addition to the photoactive region, there can be one or morefurther layers. These include, for example, layers withelectron-conducting properties (electron transport layer, ETL); layerswhich comprise a hole-conducting material (hole transport layer, HTL);exciton- and hole-blocking layers (e.g. EBLs) which should not absorband multiplication layers. The role of the EBLs is to prevent damage ofthe acceptor layer due to cathode evaporation; eliminate undesiredexciton quenching at the electron-acceptor/cathode interface; andprovide a spacer between the photoactive region and reflecting cathode,thereby increasing the optical intensity at the donor-acceptor interfaceand, thus, the light absorption efficiency.

Suitable exciton- and hole-blocking layers are described, for example,in U.S. Pat. No. 6,451,415. Suitable materials for exciton blockerlayers are, for example, bathocuproin (BCP),4,4′,4″-tris[3-methylphenyl-N-phenylamino]triphenylamine (m-MTDATA) orpolyethylenedioxy-thiophene (PEDOT).

In one aspect, a solar cell can comprise at least one photoactivedonor-acceptor heterojunction. Upon optical excitation of an organicmaterial, excitons are generated. For photocurrent to occur, theelectron-hole pair has to be separated, typically at a donor-acceptorinterface between two dissimilar contacting materials. At such aninterface, the donor material forms a heterojunction with an acceptormaterial. If the charges do not separate, they can recombine in ageminate recombination process, also known as quenching, eitherradioactively, by the emission of light of a lower energy than theincident light, or non-radioactively, by the production of heat. Eitherof these outcomes is undesirable. In one aspect, when at least onecompound of the general molecular structure (I) and/or (II) is used asthe charge generating (donor) as well as HTM (hole transport material),and/or the corresponding electron accepting ETM (electron transportmaterial) can be selected such that, after excitation of the compounds,a rapid electron transfer to the ETM takes place. Suitable ETMs are, forexample, C60 and other fullerenes, perylene-3,4;9,10-bis(dicarboximides)(PTCDIs), etc.

In one aspect, the heterojunction can have a planar configuration (PHJ)(cf. Two layer organic photovoltaic cell, C. W. Tang, Appl. Phys. Lett.,48 (2), 183-185 (1986) or N. Karl, A. Bauer, J. Holzapfel, J.Marktanner, M. Mobus, F. Stolzle, Mol. Cryst. Liq. Cryst., 252, 243-258(1994), M. V. Martinez-diaz, G. de la Toree, T. Tones, ChemChomm.,7090-7108 (2010)).

In another aspect, the heterojunction can be implemented as a bulkheterojunction (BHJ) or interpenetrating donor-acceptor network. Organicphotovoltaic cells with a bulk heterojunction are e.g. described by C.J. Brabec, N. S. Sariciftci, J. C. Hummelen in Adv. Funct. Mater., 11(1), 15 (2001) or by J. Xue, B. P. Rand, S. Uchida and S. R. Forrest inJ. Appl. Phys. 98, 124903 (2005), M. V. Martinez-diaz, G. de la Toree,T. Tones, ChemChomm., 7090-7108 (2010).

In another aspect, the compounds of the general molecular structure (I)and/or (II) can be used as a photoactive material in solar cells withM-i-M, p-i-n, p-n, M-i-p or M-i-n structure (M=metal, p=p-doped organicor inorganic semiconductor, n=n-doped organic or inorganicsemiconductor, i=intrinsically conductive system of organic layers; cf.,for example, J. Drechsel et al., Org. Electron., 5 (4), 175 (2004) orMaennig et al., Appl. Phys. A 79, 1-14 (2004)).

In another aspect, the compounds of the general molecular structure (I)and/or (II) can also be used as a photoactive material in tandem cells.Tandem cells comprise two combined unit cells, each one being atwo-layer organic solar cell. Suitable tandem cells are described e.g.by P. Peumans, A. Yakimov, S. R. Forrest in J. Appl. Phys, 93 (7),3693-3723 (2003) (cf. U.S. Pat. No. 4,461,922, U.S. Pat. No. 6,198,091and U.S. Pat. No. 6,198,092) and are discussed in details below.

The compounds of the general molecular structure (I) and/or (II) canalso be used as a photoactive material in tandem cells composed of twoor more M-i-M, p-i-n, M-i-p or M-i-n diodes stacked on one another (cf.patent application DE 103 13 232.5) (J. Drechsel et al., Thin SolidFilms, 451452, 515-517 (2004)).

In another aspect, the layer thicknesses of the M, n, i and p layers canrange from about 10 to about 1,000 nm. Thin layers can be produced byvapor deposition under reduced pressure or in inert gas atmosphere, bylaser ablation or by solution- or dispersion-processable methods such asspin-coating, knife-coating, casting methods, spraying, dip-coating orprinting (e.g. inkjet, flexographic, offset, gravure; intaglio,nano-imprinting).

In order to improve efficiency of an organic solar cell, the averagedistance an exciton can diffuse from its generation to its dissociationsite (donor-acceptor interface) can be reduced in an interpenetratingnetwork of the donor and acceptor materials. In one aspect, a morphologyof a bulk-heterojunction is characterized by a great donor-acceptorinterface area and continuous carrier conducting pathways to theopposing electrodes.

Bulk heterojunctions can be produced by a gas phase deposition process(physical vapor deposition, PVD). Suitable methods are described in US2005/0227406, to which reference is made here. To this end, typically acompound of general molecular structure (I) and/or (II) as electrondonor and at least one electron acceptor material can be subjected to avapor phase deposition by co-sublimation. PVD processes are performedunder high-vacuum conditions and comprise the following steps:evaporation, transport, deposition.

In another aspect, other layers of solar cell can be produced by knownmethods, such as, for example, vapor deposition under reduced pressureor in inert gas atmosphere, by laser ablation or by solution- ordispersion-processable methods such as spin-coating, knife-coating,casting methods, spraying, dip-coating or printing (e.g. inkjet,flexographic, offset, gravure; intaglio, nano-imprinting). In anotheraspect, a complete solar cell can be produced by a gas phase depositionprocess.

In another aspect, the photoactive region (homogeneous layers or mixedlayer) can be subjected to a thermal treatment directly after itspreparation or after the preparation of other layers being part of thesolar cell Annealing can improve the morphology of the photoactiveregion. In addition or alternatively to a thermal treatment, thephotoactive region can be subjected to a treatment using asolvent-containing gas. In one aspect, saturated solvent vapors in airat ambient temperature are used. Suitable solvents can comprise toluene,xylene, chlorobenzene, trichloromethane, dichloromethane,N-methylpyrrolidone, N,N-dimethylformamide, ethyl acetate and mixturesthereof.

The disclosed compounds and methods for preparing said compounds andarticles of manufacture made therefrom include at least the followingaspects:

Aspect 1: A compound of a general molecular structure (I):

wherein M comprises silicon, germanium, tin, or a combination thereof;wherein “n” is an integer equal to or greater than 0; wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ comprises an optionally substitutedaryl containing group comprising from greater than or equal to about 6to about 22 carbon atoms, wherein aryl containing group, if substituted,can be substituted at one or more positions with one or more of the sameor different heteroatoms comprising a halogen, oxygen, sulfur, nitrogen,or a combination thereof.

Aspect 2: The compound of Aspect 1, wherein n ranges from about 0 toabout 4.

Aspect 3: The compound of Aspect 1, wherein R₂ comprises an optionallysubstituted aryl containing group comprising from greater than or equalto about 6 to about 18 carbon atoms, wherein if substituted, can besubstituted at one or more positions with one or more of the same ofdifferent hetero atoms.

Aspect 4: The compound of Aspect 1, wherein R₂ does not comprise ametal.

Aspect 5: The compound of Aspect 1, wherein R₂ does not comprise aheteroatom as a bridging group.

Aspect 6: The compound of Aspect 1, wherein R₂ comprises a halogencomprising fluorine, chlorine, bromine, iodine, or a combinationthereof.

Aspect 7: The compound of Aspect 6, wherein R₂ does not comprisechlorine.

Aspect 8: The compound of Aspect 6, wherein R₂ comprises chlorine, andwherein the aryl containing group, if substituted, cannot be substitutedat a para-position.

Aspect 9: The compound of Aspect 6, wherein R₂ comprises chlorine, andwherein the aryl containing group, if substituted, is substituted at oneor more ortho-positions.

Aspect 10: A compound of a general molecular structure (II):

wherein M comprises silicon, germanium, tin, or a combination thereof,wherein “n” is an integer equal to or greater than 0; wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an alkylaryl group, an arylalkylgroup, an akylene group, a hydrogen, a halogen, or a combinationthereof; and wherein R₂ and R₃ are the same or different and comprise ahalogen, oxygen, sulfur, nitrogen, aryl or an optionally substitutedaryloxy containing group comprising from greater than or equal to about6 to about 22 carbon atoms, wherein aryl containing group, ifsubstituted, can be substituted at one or more positions with one ormore of the same or different heteroatoms comprising a halogen, oxygen,sulfur, nitrogen, or a combination thereof.

Aspect 11: The compound of Aspect 10, wherein n ranges from about 0 toabout 4.

Aspect 12: The compound of Aspect 10, wherein R₂ and R₃ are the same ordifferent and comprise an optionally substituted aryloxy containinggroup comprising from greater than or equal to about 6 to about 18carbon atoms, wherein if substituted, can be substituted at one or morepositions with one or more of the same of different heteroatoms.

Aspect 13: The compound of Aspect 10, wherein R₂ and R₃ do not comprisea metal.

Aspect 14: The compound of Aspect 10, wherein R₂ and R₃ do not comprisea heteroatom as a bridging group.

Aspect 15: The compound of Aspect 10, wherein R₂ and R₃ comprises ahalogen comprising fluorine, chlorine, bromine, iodine, or a combinationthereof.

Aspect 16: The compound of Aspect 15, wherein R₂ and R₃ does notcomprise chlorine.

Aspect 17: The compound of Aspect 15, wherein R₂ and R₃ comprisechlorine, and wherein the aryl containing group, if substituted, cannotbe substituted at a para-position.

Aspect 18: The compound of Aspect 15, wherein R₂ and R₃ comprisechlorine, and wherein the aryl containing group, if substituted, issubstituted at one or more ortho-positions.

Aspect 19: A method for preparing a compound of the general molecularstructure (I) comprising the steps of: a) providing a compoundcomprising a halogen-metal bond containing R₁ substitutedphthalocyanines precursor, wherein the halogen comprises chlorine,bromine, iodine, fluorine, or a combination thereof; and wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; b) providing a reactant comprising an optionallysubstituted aryl (—R₂) or an optionally substituted arylalcohol group(OH—R₂), wherein R₂ comprises from greater than or equal to about 6 toabout 22 carbon atoms, and c) reacting the compound comprising ahalogen-metal bond containing phthalocyanines precursor and the reactantin the presence of an organic solvent under conditions effective to formthe compound of the general molecular structure (I), wherein thecompound of the general molecular structure (I) is non-soluble,negligibly soluble, partially soluble in an organic solvent, or at leastpartially soluble in an organic solvent.

Aspect 20: The method of Aspect 19, wherein the reactant comprises anoptionally substituted aryl (—R₂) or optionally substituted arylalcoholgroup (OH—R₂), wherein R₂ comprises from greater than or equal to about6 to about 18 carbon atoms.

Aspect 21: The method of Aspect 19, wherein the organic solventcomprises toluene, dimethylsulfoxide, dichloromethane.

Aspect 22: A method for preparing a compound of the general molecularstructure (II) comprising the steps of: a) providing a compoundcomprising a halogen-metal bond containing R₁ substitutedphthalocyanines precursor, wherein the halogen comprises chlorine,bromine, iodine, fluorine, or a combination thereof, and wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; b) providing a reactant comprising R₂ and/or R₃moieties, wherein R₂ and R₃ are the same or different and comprise ahalogen, oxygen, sulfur, nitrogen, or an optionally substituted aryloxycontaining group comprising from greater than or equal to about 6 toabout 22 carbon atoms; and (c) reacting the compound comprising ahalogen-metal bond containing phthalocyanines precursor and the reactantin the presence of an organic solvent under conditions effective to formthe compound of the general molecular structure (II), wherein thecompound of the general molecular structure (II) is non-soluble,negligibly soluble, partially soluble in an organic solvent, or at leastpartially soluble in an organic solvent.

Aspect 23: The method of Aspect 22, wherein R₂ and/or R₃ moieties areadded simultaneously or in a plurality of steps.

Aspect 24: The method of Aspect 22, wherein R₂ and R₃ are the same ordifferent and comprise an optionally substituted aryloxy containinggroup comprising from greater than or equal to about 6 to about 18carbon atoms.

Aspect 25: The method of Aspect 22, wherein the organic solventcomprises toluene, dimethylsulfoxide, dichloromethane, or a combinationthereof.

Aspect 26: A photovoltaic cell comprising a compound having the generalmolecular structure (I)

wherein M comprises silicon, germanium, tin, or a combination thereof;wherein “n” is an integer equal to or greater than 0; wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an aryl group, an alkylaryl group,an arylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ comprises an optionally substitutedaryl containing group comprising from greater than or equal to about 6to about 22 carbon atoms, wherein aryl containing group, if substituted,can be substituted at one or more positions with one or more of the sameor different heteroatoms comprising a halogen, oxygen, sulfur, nitrogen,or a combination thereof.

Aspect 27: A photovoltaic cell comprising a compound having the generalmolecular structure (II)

wherein M comprises silicon, germanium, tin, or a combination thereof,wherein “n” is an integer equal to or greater than 0; wherein each R₁independently comprises a straight chain alkyl group, a branched alkylgroup, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryloxy group, heterocyclic group, a monocyclic aromaticgroup, a polycyclic aromatic group, an alkylaryl group, an arylalkylgroup, an akylene group, a hydrogen, a halogen, or a combinationthereof; and wherein R₂ and R₃ are the same or different and comprise ahalogen, oxygen, sulfur, nitrogen, aryl or an optionally substitutedaryloxy containing group comprising from greater than or equal to about6 to about 22 carbon atoms, wherein aryl containing group, ifsubstituted, can be substituted at one or more positions with one ormore of the same or different heteroatoms comprising a halogen, oxygen,sulfur, nitrogen, or a combination thereof.

It is to be understood that the aspects described herein are not limitedto the specific compositions, articles, devices, systems, and/or methodsdisclosed unless otherwise specified, as such can, of course, vary. Itis also to be understood that the terminology used herein is for thepurpose of describing particular aspects only and is not intended to belimiting.

The description of the invention is also provided as an enablingteaching of the invention in its best, currently known embodiment. Tothis end, those of ordinary skill in the relevant art will recognize andappreciate that changes and modification can be made to the variousaspects of the invention described herein, while still obtaining thebeneficial results of the present invention. It will also be apparentthat some of the desired benefits of the present invention can beobtained by selection some of the features of the present inventionwithout utilizing other features. Accordingly, those of ordinary skillin the relevant art will recognize that many modification andadaptations of the present invention are possible and can even bedesirable in certain circumstances and are thus also a part of thepresent invention. Thus, the following description is provided asillustrative of the principles of the present invention and not inlimitation thereof.

Various combinations of elements of this disclosure are encompassed bythis invention, e.g. combinations of elements from dependent claims thatdepend upon the same independent claim.

Moreover, it is to be understood that unless otherwise expressly stated,it is in no way intended that any method set forth herein be construedas requiring that its steps be performed in a specific order.Accordingly, where a method claim does not actually recite an order tobe followed by its steps or it is not otherwise specifically stated inthe claims or descriptions that the steps are to be limited to aspecific order, it is no way intended that an order be inferred, in anyrespect. This holds for any possible non-express basis forinterpretation, including: matters of logic with respect to arrangementof steps or operational flow; plain meaning derived from grammaticalorganization or punctuation; and the number or type of embodimentsdescribed in the specification.

All publications mentioned herein are incorporated herein by referenceto disclose and describe the methods and/or materials in connection withwhich the publications are cited.

It is also to be understood that the terminology used herein is for thepurpose of describing particular aspects only and is not intended to belimiting. As used in the specification and in the claims, the term“comprising” can include the aspects “consisting of” and “consistingessentially of.” Unless defined otherwise, all technical and scientificterms used herein have the same meaning as commonly understood by one ofordinary skill in the art to which this invention belongs. In thisspecification and in the claims which follow, reference will be made toa number of terms which shall be defined herein.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an aromaticcompound” includes mixtures of two or more such aromatic compounds.Furthermore, for example, reference to a filler includes mixtures offillers.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another aspect includes from the one particular value and/orto the other particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another aspect. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint. It is also understood that there are a number of valuesdisclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed. It is also understood that each unit between two particularunits are also disclosed. For example, if 10 and 15 are disclosed, then11, 12, 13, and 14 are also disclosed.

Disclosed are materials, compounds, compositions, and components thatcan be used for, can be used in conjunction with, can be used inpreparation for, or are products of the disclosed method andcompositions. These and other materials are disclosed herein, and it isunderstood that when combinations, subsets, interactions, groups, etc.of these materials are disclosed that while specific reference of eachvarious individual and collective combinations and permutation of thesecompounds cannot be explicitly disclosed, each is specificallycontemplated and described herein. For example, if a particular compoundis disclosed and discussed and a number of modifications that can bemade to a number of R groups are discussed, each and every combinationand permutation of the inhibitor and the modifications to its R groupthat are possible are specifically contemplated unless specificallyindicated to the contrary. Thus, if a class of molecules A, B, and C aredisclosed as well as a class of molecules D, E, and F and an example ofa combination molecule, A-D is disclosed, then even if each is notindividually recited, each is individually and collectivelycontemplated. Thus, in this example, each of the combinations A-E, A-F,B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated andshould be considered disclosed from disclosure of A, B, and C; D, E, andF; and the example combination A-D. Likewise, any subset or combinationof these is also specifically contemplated and disclosed. Thus, forexample, the sub-group of A-E, B-F, and C-E are specificallycontemplated and should be considered disclosed from disclosure of A, B,and C; D, E, and F; and the example combination A-D. This conceptapplies to all aspects of this disclosure including, but not limited to,steps in methods of making and using the disclosed compositions. Thus,if there are a variety of additional steps that can be performed it isunderstood that each of these additional steps can be performed with anyspecific embodiment or combination of embodiments of the disclosedmethods, and that each such combination is specifically contemplated andshould be considered disclosed.

In this specification and in the claims which follow, reference will bemade to a number of terms which shall be defined to have the followingmeanings:

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not. For example, the phrase “optionally substituted lower alkyl”means that the lower alkyl group can or cannot be substituted and thatthe description includes both unsubstituted lower alkyl and lower alkylwhere there is substitution.

As used herein, the term or phrase “effective,” “effective amount,” or“conditions effective to” refers to such amount or condition that iscapable of performing the function or property for which an effectiveamount is expressed. As will be pointed out below, the exact amount orparticular condition required can vary from one aspect to another,depending on recognized variables such as the materials employed and theprocessing conditions observed. Thus, it is not always possible tospecify an exact “effective amount” or “condition effective to.”However, it should be understood that an appropriate effective amountwill be readily determined by one of ordinary skill in the art usingonly routine experimentation.

A weight percent of a component, unless specifically stated to thecontrary, is based on the total weight of the general molecularstructure or composition in which the component is included. For exampleif a particular element or component in a composition or article is saidto have 8% weight, it is understood that this percentage is relation toa total compositional percentage of 100%.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valence filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill in the art to which this inventionbelongs.

The term “Pc” as used herein is intended to refer to a phthalocyaninemoiety, unless specifically stated to the contrary, and such aphthalocyanine moiety can comprise any phthalocyanine moiety, derivativeor analogue thereof.

The term “alkyl group” as used herein is a branched or unbranchedsaturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl,heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and thelike. A “lower alkyl” group is an alkyl group containing from one to sixcarbon atoms.

The term “alkoxy” as used herein is an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group can bedefined as —OR where R is alkyl as defined above. A “lower alkoxy” groupis an alkoxy group containing from one to six carbon atoms.

The term “alkenyl group” as used herein is a hydrocarbon group of from 2to 24 carbon atoms and structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (AB)C═C(CD) areintended to include both the E and Z isomers. This can be presumed instructural formulae herein wherein an asymmetric alkene is present, orit can be explicitly indicated by the bond symbol C.

The term “alkynyl group” as used herein is a hydrocarbon group of 2 to24 carbon atoms and a structural formula containing at least onecarbon-carbon triple bond.

The term “aryl group” as used herein is any carbon-based aromatic groupincluding, but not limited to, benzene, naphthalene, etc. The term“aromatic” also includes “heteroaryl group,” which is defined as anaromatic group that has at least one heteroatom incorporated within thering of the aromatic group. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group canbe substituted or unsubstituted. The aryl group can be substituted withone or more groups including, but not limited to, alkyl, alkynyl,alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy,carboxylic acid, or alkoxy.

The term “cycloalkyl group” as used herein is a non-aromaticcarbon-based ring composed of at least three carbon atoms. Examples ofcycloalkyl groups include, but are not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, etc. The term “heterocycloalkylgroup” is a cycloalkyl group as defined above where at least one of thecarbon atoms of the ring is substituted with a heteroatom such as, butnot limited to, nitrogen, oxygen, sulfur, or phosphorus.

The term “aralkyl” as used herein is an aryl group having an alkyl,alkynyl, or alkenyl group as defined above attached to the aromaticgroup. An example of an aralkyl group is a benzyl group.

The term “hydroxyalkyl group” as used herein is an alkyl, alkenyl,alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, orheterocycloalkyl group described above that has at least one hydrogenatom substituted with a hydroxyl group.

The term “alkoxyalkyl group” is defined as an alkyl, alkenyl, alkynyl,aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl groupdescribed above that has at least one hydrogen atom substituted with analkoxy group described above.

The compounds disclosed herein can, independently, possess two or moreof the groups listed above. For example, if R₁ is a straight chain alkylgroup, one of the hydrogen atoms of the alkyl group can be substitutedwith a hydroxyl group, an alkoxy group, etc. Depending upon the groupsthat are selected, a first group can be incorporated within second groupor, alternatively, the first group can be pendant (i.e., attached) tothe second group. For example, with the phrase “an alkyl groupcomprising an ester group,” the ester group can be incorporated withinthe backbone of the alkyl group. Alternatively, the ester can beattached to the backbone of the alkyl group. The nature of the group(s)that is (are) selected will determine if the first group is embedded orattached to the second group.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompounds, compositions, articles, devices, and/or methods described andclaimed herein are made and evaluated, and are intended to be purelyexemplary and are not intended to limit the scope of what the inventorsregard as their invention. Efforts have been made to ensure accuracywith respect to numbers (e.g., amounts, temperature, etc.) but someerrors and deviations should be accounted for. Unless indicatedotherwise, parts are parts by weight, temperature is in ° C. or is atambient temperature, and pressure is at or near atmospheric. There arenumerous variations and combinations of reaction conditions, e.g.,component concentrations, desired solvents, solvent mixtures,temperatures, pressures and other reaction ranges and conditions thatcan be used to optimize the product purity and yield obtained from thedescribed process. Only reasonable and routine experimentation will berequired to optimize such process conditions.

Example 1

In a first example, group IV metal-phthalocyanines (Pcs) functionalizedwith m-cresol, as model phenoxy groups, were successfully synthesized(Scheme 1). All group IV Pcs were characterized by UV-Vis spectroscopyand cyclic voltammetry.

In one aspect, various methods can be utilized to synthesize thephthalocyanines (Pc) containing group IV metals described herein thatare soluble in organic solvents. The previous methodology of engineeringthe solid state arrangement of subphthalocyanines (Ind. Eng. Chem. Res.2011, 50, 10910) can be extended to the synthesis of phthalocyanines(Pc) containing group IV metal. The chloride-metal bond of the group IVmetal containing Pc (MPcs) precursor is amenable to the displacement ofthe chloride ion with a nucleophile like a phenoxide group.

For example a mixture of Cl₂-SiPc (0.50 g, 0.82 mmol) and m-cresol (3.20g, 29.63 mmol) can be added to 25 mL of Toluene in an oven dried anddegassed 100 ml glass reactor. The reaction mixture can then be heatedto 115° C. overnight under ultra-pure N₂ gas. The crude product can becooled to room temperature prior to being washed by basic aqueoussolution (2M KOH) to remove excess phenol and dried under vacuum. Insome cases the functionalized Pc can be washed with isopropanol(optionally ultrasonicated) and filtered to remove excess phenol. Theresulting product (0.25 g, 0.33 mmol, yield: 40%) was characterized by¹H NMR spectroscopy (DMSO) and DART mass spectroscopy. Using similarconditions, m-cresol derivatives of GePc and SnPc (Scheme 1) could besynthesized in chlorobenzene and toluene.

UV-Vis Spectroscopy of Group IV Phthalocyanines Functionalized withm-Cresol:

UV-Vis spectroscopy can be performed in toluene. As an example, thecorresponding UV-Vis absorbance spectras for the group IV metalcontaining Pcs can be found in FIG. 1 and the corresponding λ_(MAX) canalso be found in Table 1 for all the soluble compounds. (m-cresol)₂-SiPcand (m-cresol)₂-GePc exhibited similar absorbance maximums, λ_(MAX)=679nm and λ_(MAX)=676 nm. A slight red shift was observed for (PDP)₂—SnPcto λ_(MAX)=691 nm.

Cyclic Voltammetry of Group IV Metal Containing Phthalocyanines (Pcs):

Cyclic voltammetry (CV) was performed using a three-electrode cellassembly at room temperature in a 0.1 M tetrabutylammonium perchlorate(TBAP) in dichloromethane electrolyte solution. The working electrodewas a glassy carbon disk electrode, the counter electrode was a polishedplatinum wire and the reference electrode was Ag/AgCl. An internalstandard of bis(pentamethylcyclopentadienyl)iron (E_(1/2,red)=0.012 V)and a scan rate was 100 mV/s was used for all measurements. The sampleswere bubbled using nitrogen until no dissolved oxygen was present (20-30minutes prior to each run). The characteristic cyclic voltammograms foreach group IV metal containing Pcs can be found in FIG. 1. The resultsfrom the CV measurements can also be found in Table 1, as reported interms of the peak oxidations (E_(Peak) ^(ox)), the peak reductions(E_(Peak) ^(red)), the half peak oxidation (E_(1/2) ^(ox)) and the halfpeak reduction (E_(1/2) ^(red)). Finally as a comparison all the highestoccupied molecular orbitals (E_(HOMO)s) corresponding to the group IVmetal containing Pcs were calculated from a reported empiricalrelationship

E_(HOMO)=−(1.4±0.1)×(E_(1/2) ^(ox))−(4.6±0.08) eV (Dandrade et al.Organic Electronics 2005, 6, 11-20) and are reported in Table 1.

Oxidative scanning of (m-cresol)₂-SiPc reveals an completely reversiblepeak at +1.148 V, which is used to calculate a HOMO level of −6.1 eV.Reductive scanning of the compound reveals multiple reversible processesat −0.507 V and −0.690 V and a third less noticeable one at >−0.9 V(FIG. 2, Table 1). Similarly, the oxidative scanning of (m-cresol)₂-GePcalso reveals a completely reversible peak at +0.586 V, which is used tocalculate a HOMO level of −5.3 eV. Reductive scanning of the compoundreveals multiple reversible process at −0.493 V and −0.915 V (FIG. 2,Table 1). (PDP)₂—SnPc was soluble in DCM for analysis and it's cyclicvoltammogram can be found in FIG. 2. The oxidative scanning of(PDP)₂—SnPc reveals an irreversible peak at +1.135 V, which is used tocalculate a HOMO level of −6.2 eV. The reductive scanning of the solubletin-containing compound revealed two reversible processes at −0.371 Vand −0.854 V (FIG. 2, Table 1).

In addition the band gap (E_(Gap,Opt)) can be estimated from the opticalabsorbance data using the following equation:

$E_{{Gap},{Opt}} = \frac{h \cdot C}{\lambda}$

where h is planks constant, C is the speed of light and A is the cut-offwavelength of the UV-Vis absorbance spectra. Therefore the lowestoccupied molecular orbital can be estimated between the difference ofE_(HOMO) and E_(Gap,Opt). Both E_(HOMO) and E_(Gap,Opt) and the maxabsorbance (λ_(MAX)) can all be found in Table 1.

TABLE 1 Electrochemical and optical characterization of group IV metalcontaining phthalocyanines. E_(Peak) ^(ox) E_(Peak) ^(red) E_(1/2) ^(ox)E_(1/2) ^(red) E_(HOMO) ¹ E_(Gap,Opt) ² λ_(MAX) Sample ID (mV) (mV) (mV)(mV) (eV) (eV) E_(LUMO) ³ (eV) (nm) (mCresol)₂-SiPc 1148 −507, −690 1098−560, −770 −6.1 1.8 −4.4 682 (mCresol)₂-GePc  586 −493, −915  478 −556,−956 −5.3 1.8 −3.5 677 (PDP)₂-SnPc 1135 (irv.) −339, −816 — −371, −854−6.2 1.7 −4.5 691 ¹E_(HOMO) = −(1.4 ± 0.1) · (E_(1/2) ^(ox)) − (4.6 ±0.08) eV (Dandrade et al. Organic Electronics 2005, 6, 11-20)²E_(Gap,Opt) was determined using E_(Gap,Opt) = h * C/λ, where h isplanks constant, C is the speed of light and λ is the cut off wavelengthof the absorbance spectra. ³E_(LUMO) = E_(HOMO) ⁻ E_(Gap,Opt)

Throughout this application, various publications are referenced. Thedisclosures of these publications in their entireties are herebyincorporated by reference into this application in order to more fullydescribe the compounds, compositions and methods described herein.

Various modifications and variations can be made to the compounds,compositions and methods described herein. Other aspects of thecompounds, compositions and methods described herein will be apparentfrom consideration of the specification and practice of the compounds,compositions and methods disclosed herein. It is intended that thespecification and examples be considered as exemplary.

1-27. (canceled)
 28. A planar donor-acceptor heterojunction comprising atwo layer photoactive region, wherein each layer has a homogeneouscomposition and the two layers form the planar donor-acceptorheterojunction, wherein at least one of the layers includes a compoundhaving the general molecular structure (I):

wherein M is silicon, germanium, tin, or a combination thereof; wherein“n” is an integer equal to or greater than 0; wherein each R₁independently is a straight chain alkyl group, a branched alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group,an aryloxy group, heterocyclic group, a monocyclic aromatic group, apolycyclic aromatic group, an aryl group, an alkylaryl group, anarylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ is a substituted aryl containinggroup having from greater than or equal to about 6 to about 10 carbonatoms.
 29. The planar donor-acceptor heterojunction of claim 28, whereinn ranges from about 0 to
 4. 30. The planar donor-acceptor heterojunctionof claim 28, wherein the substituted aryl containing group has 7 carbonatoms.
 31. The planar donor-acceptor heterojunction of claim 28, whereinR₂ does not comprise a metal.
 32. The planar donor-acceptorheterojunction of claim 28, wherein R₂ does not comprise a heteroatom asa bridging group.
 33. The planar donor-acceptor heterojunction of claim28, wherein R₂ further comprises a heteroatom, wherein the heteroatom isa halogen selected from a group consisting essentially of fluorine,chlorine, bromine, iodine, and a combination thereof.
 34. The planardonor-acceptor heterojunction of claim 28, wherein n is 1, and R₂ is a3-methyl aryl containing group.
 35. The planar donor-acceptorheterojunction of claim 28, wherein n is 1, and R₂ is substituted at oneor more ortho positions with a methyl group, ethyl group or propylgroup.
 36. The planar donor-acceptor heterojunction of claim 28, whereinthe photoactive region is disposed on a substrate.
 37. The planardonor-acceptor heterojunction of claim 36, wherein the substrate iscomprised in a photovoltaic cell.
 38. A photovoltaic cell comprising aplanar donor-acceptor heterojunction comprising a compound having thegeneral molecular structure as claimed in claim
 28. 39. A planardonor-acceptor heterojunction comprising a two layer photoactive region,wherein each layer has a homogeneous composition and the two layers formthe planar donor-acceptor heterojunction, wherein at least one of thelayers includes a compound having the general molecular structure (II):

wherein M is silicon, germanium, tin, or a combination thereof; wherein“n” is an integer equal to or greater than 0; wherein each R₁independently is a straight chain alkyl group, a branched alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group,an aryloxy group, heterocyclic group, a monocyclic aromatic group, apolycyclic aromatic group, an aryl group, an alkylaryl group, anarylalkyl group, an akylene group, a hydrogen, a halogen, or acombination thereof; and wherein R₂ and R₃ are the same or different andare a halogen, oxygen, sulfur, nitrogen, or an aryloxy containing groupand at least one of the R₂ and R₃ is a substituted aryloxy containinggroup having from 6 to about 10 carbon atoms.
 40. The planardonor-acceptor heterojunction of claim 39, wherein n ranges from about 0to
 4. 41. The planar donor-acceptor heterojunction of claim 39, whereinthe substituted aryloxy containing group has 7 carbon atoms.
 42. Theplanar donor-acceptor heterojunction of claim 39, wherein R₂ and R₃ doesnot comprise a metal.
 43. The planar donor-acceptor heterojunction ofclaim 39, wherein R₂ and R₃ does not comprise a heteroatom as a bridginggroup.
 44. The planar donor-acceptor heterojunction of claim 39, whereinR₂ and R₃ further comprises a heteroatom, wherein the heteroatom is ahalogen selected from a group consisting essentially of fluorine,chlorine, bromine, iodine, and a combination thereof.
 45. The planardonor-acceptor heterojunction of claim 39, wherein n is 1, and R₂ and R₃are the same and the substituted aryloxy containing group is a 3-methylaryl containing group.
 46. The planar donor-acceptor heterojunction ofclaim 39, wherein n is 1, R₁ is hydrogen, and the substituted aryloxycontaining group is a 3-methyl aryl containing group.
 47. The planardonor-acceptor heterojunction of claim 39, wherein n is 1, and thesubstituted aryloxy containing group is substituted at one or more orthopositions with a methyl group, ethyl group or propyl group.
 48. Theplanar donor-acceptor heterojunction of claim 39, wherein photoactiveregion is disposed on a substrate comprised in a photovoltaic cell. 49.A photovoltaic cell comprising a planar donor-acceptor heterojunctioncomprising a compound having the general molecular structure as claimedin claim 39.